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DIM360 - Ver 2.5 (21 Aug 1997) 2720000/0
The file contains technical information submitted after the application was filed and not included in this specification
0072830
NEW EUROPEAN PATENT SPECIFICATION
B2
19890419
EP
82900560.2
19820225
19830124
19840612
19890419
en
en
en
8106055
19810226
GB
19890419
198916
19830302
198309
19851121
198547
19850207
19890419
198916
4
4H 05K 3/00 A
de
VERFAHREN ZUR BEHANDLUNG VON KUPFERFOLIE
en
TREATMENT OF COPPER FOIL
fr
TRAITEMENT D'UNE FEUILLE DE CUIVRE
FR-A- 2 019 772
FR-A- 2 148 025
FR-A- 2 156 030
GB-A- 1 515 361
GB-A- 2 030 176
US-A- 3 585 010
US-A- 4 234 395
TORDAY, John
23 North Avenue
Gosforth Newcastle upon Tyne
GB
BUSH, Michael Edward
7 Melbourne Crescent
Whitley Bay Tyne & Wear
GB
Electrofoils Technology Limited
00770490
SJA/31628/004
Cookson House Willington Quay
Wallsend, Tyne & Wear NE28 6UQ
GB
Allard, Susan Joyce
et al
00027611
BOULT WADE TENNANT, 27 Furnival Street
London EC4A 1PQ
GB
01
19860809
1
TREFIMETAUX
00015770
6, Boulevard Général Leclerc
F-92115 Clichy
FR
Pascaud, Claude
00039171
PECHINEY 28, rue de Bonnel
69433 Lyon Cédex 3
FR
DE
FR
GB
GB8200066
19820225
en
WO8202991
19820902
198221
19830302
198309

Technical field
The present invention relates to a method of treating copper foil, which may be rolled or, preferably, electroplated, for use in the production of printed circuit boards to improve the foil's adhesion to a base material, and to laminates formed as a result of said treatment.

Background art
Copper foil used in the manufacture of printed circuit boards is usually bonded to a dielectric base material and various proposals have been made for improving the strength of the bond between the copper foil and the base material.
It is now well-established practice to apply copper dendrites to the matt surface of the foil, said dendrites often being reinforced or partially encapsulated with a continuous, coherent layer of copper. In for example US patent specification No. 3 220 897 there is disclosed a copper foil which has been treated electrolytically to provide it with a nodularised surface for better adhesion while US patent specification No. 3 293 109 discloses a copper foil provided with minute projections containing copper copper-oxide particles on its surface, said projections being encapsulated by a copper coating. Several subsequent electro-deposited layers may then follow to achieve a bond of desired strength and one which will be largely unaffected by soldering. Metallic layers of, for example, zinc, brass or nickel may be present to separate the copper dendrites from the reactive resins in the dielectric base material.
It is often difficult to control the size and distribution of the dendrites in the primary copper layer and it has therefore been proposed to add various agents to the copper of said layer in an attempt to effect such control, a preferred additive being arsenic. In such a case, a nodular or dendritic layer of metal comprising an alloy of oxidised copper with arsenic is electro-deposited onto a matt surface of the copper foil from a bath containing copper sulphate and arsenic values.
However, reliable control in the growth of the dendrites, particularly the larger dendrites, is still not completely satisfactory.

Disclosure of the invention
According to the present invention there is provided a method of treating copper foil comprising the steps of depositing onto the foil at least one nodular or dendritic layer of metal to improve the bond strength of the foil with an associated base material, encapsulating said layer with one or more layers of metal, such as, copper, arsenic, bismuth, brass, bronze, nickel, cobalt or zinc or alloys or co-deposits of such metals, and applying over the outermost encapsulating layer a further layer containing zinc characterised in that the or each nodular or dendritic layer is of zinc and is deposited directly onto a matt surface of the foil and in that the further layer comprises an alloy of zinc and nickel or of zinc and cobalt.
The presence of encapsulating layers, which are of continuous, coherent metal as opposed to a powdery or microcrystalline dendritic deposit, can result in an increased peel strength when bonded to glass-epoxy boards compared with foil without such encapsulation of the dendrites, and furthermore ensures that, under conditions of strong resin flow during lamination - such as high pressure and temperature conditions which can cause certain epoxy resins to flow pior to setting hard - no zinc dendrites are detached from the primary layer to become embedded in the resin mass.
The further layer is preferably nodular or dendritic and is preferably an alloy of zinc and nickel, although an alloy of zinc and cobalt could be used. The amount of nickel in the alloy is conveniently within the range 3 to 15 % and is preferably of the order of 10 %. The provision of such a further layer increases the bond strength of the foil with a dielectric base material compared with a foil without said outer layer. Such layers are normally thinner than those applied as the innermost layer next to the basic copper foil matt.
In one embodiment according to the invention, the treatment comprises the steps of deposition onto a matt surface of he copper foil a first nodular or dendritic layer of zinc, depositing a protective layer of cyanide copper over said first nodular or dendritic layer, depositing an encapsulating layer of pyrophospate copper over said protective layer of cyanide copper, and depositing a further nodular or dendritic layer of zinc nickel alloy over said encapsulating layer.
Under some laminating conditions, when the temperature may be in excess of 165°C, there can be pronounced interdiffusion between the outermost nodular or dendritic layer of zinc alloy and the underlying copper layer which produced a canary yellow brass layer. This phenomenon is often accompanied by considerable loss of peel strength.
Accordingly, in a further embodiment the treatment includes the step of depositing a diffusion-inhibiting layer of metal underlying said further layer comprising zinc alloy. The diffusion inhibiting layer is deposited over the outermost encapsulating layer. The diffusion-inhibiting layer may comprise, for example, an alloy of copper with arsenic or bismuth or, alternatively, a weak deposit of pure arsenic or bismuth.
Thus there is provided a treatment which results in the formation of zinc dendrites as the primary adhesion-promoting layer of a copper foil to be laminated to a dielectric substrate, control in the size and distribution of the dendrites being relatively easy to achieve. The preferred zinc dendritic layers can readily be produced from a number of electrolytes of which perhaps the most economical and simple is a relatively dilute solution of sodium zincate. In general, the size of the dendrite increases proportionately with increase in zinc concentration, time of plating and current density an inversely with the temperature of the solution.
In methods in which a further, outermost nodular or dendritic layer is provided of pure zinc, there can, under certain circumstances, be problems, particularly if washing between the stages of the process is not perfect. In the case of pure zinc deposited from an alkali bath, there can be difficulties in effecting complete washing of the alkali solution, and any retained solution can interfere with the polymerisation of the epoxy layer and cause a consequent reduction in peel strength.
Further, and as mentioned above, if the outer zinc layer is deposited over a copper-based encapsulating layer, there is a tendency for the pure zinc to react with the copper whereby the zinc is converted into brass, which can result in a variability in peel strength dependent upon the nature of the conversion.
The provision of an outermost nodular or dendritic layer which is an alloy of zinc with nickel tends to obviate these problems, in that the presence of the nickel in said layer slows down or prevents the diffusion of the zinc into the underlying copper and also prevents undercut during etching (the metal of this layer being less soluble than zinc in acid).
A further method for inhibiting the conversion of the zinc of the outer layer into brass, which method may be used in addition to the incorporation of nickel into the outer layer, is, again as mentioned above, to provide a layer of or containing arsenic underlying said outer layer, although bismuth could be used in place of arsenic. Conveniently such a conversion- inhibiting layer may replace an encapsulating layer of pyrophosphate copper, although it may be included in addition to an encapsulating copper layer between said encapsulating copper layer and the outermost nodular or dendritic layer of zinc alloy. The presence of such an arsenic- based layer enhances the method of making it less sensitivie to contamination which is particularly useful in industrial processes where 100 % washing is rarely achieved.

Best modes of carrying out the invention

Example 1
The following electro-deposited layers were applied to te matt side of an electro-formed copper foil 35 µm thick, all formulae being expressed as concentrations in water:

1st layer
A bath was made up as follows:
This process produces a fine layer of zinc dendrites which covers the matt structure of the foil, producing the greatest concentration of dendrites on the peaks of the matt.

2nd layer
Before these dendrites are encapsulated by copper plating, a thin layer of cyanide-type copper plating is applied to prevent the formation of precipitated copper by the chemical replacement reaction between zinc metal and copper ion. Such a cyanide-type copper layer is conveniently deposited using the following bath:

3rd layer
A continuous, coherent layer of copper is then plated on the foil using the following bath:
A pink coloured encapsulating plating layer of sound pyrophosphate copper is deposited under the above conditions.

4th layer
An outer layer of nodular or dendritic zinc/nickel alloy is then formed using the following bath:
These conditions produce a slightly dendritic final covering layer of zinc/nickel which gives the matt surface a clean dark grey colour.
The foil is well washed by means of water sprays between each treatment stage. The overall process is carried out by passing copper foil in serpentine fashion, using both submersed and free standing rollers, through a series of plating tanks and rinsing stations. The current in each plating tank is separately controlled and the time of plating is determined by the speed of the copper web and the length of the anode used in the particular cell.
Preferably the plated foil is passed through a dilute warm solution of chromic acid which renders the shiny side of the foil passive and provides a shelf life of some months before staining of the foil occurs. This chromate treatment also stabilises the treatment surface and gives a somewhat enhanced peel strength. After treatment the foil is washed, air dried and then reeled up.
Copper foil treated in the above manner, when laminated to epoxy resin impregnated glass cloth sheets under heat and pressure, provides a laminate the peel strength of which is of the order of 19,12 to 21,08 N/cm (5 to 5.5 kp/in.) both before and after solder float. The time taken to blister when floated on solder is in excess of 5 mins. Etching with ferric chloride or persulphate type etches gives no undercut. The treatment is firm and produces no "tape transfer" and, even with very reactive resins, there is no evidence of any discolouration showing that the treatment is inert.
It is noteworthy that surprisingly good peel strength is already available after the first layer of zinc dendrite is deposited onto the copper matt. Such a single stage treatment (taking the ist layer only and passing it through dilute warm chromic acid solution) produces a copper foil having a peel strength of 15,69 - 16,18 N/cm (4 - 4.2 kp/in.) on epoxy glass laminate.
It is to be noted that the provision of an outer layer of zinc nickel alloy substantially inhibits the conversion of said layer into brass. Said layer conveniently incorporates 10 % nickel, although this percentage can be adjusted by varying the constituents of the bath.
It is however preferred to keep the percentage of nickel above 3, otherwise the degree of inhibition of conversion reaction is slight, and below 15, otherwise the resultant alloy is not etchable with commercially available etchants.

Example 2
A further means of controlling the diffusion of the zinc of the outermost layer into the underlying copper is to provide a layer containing arsenic between the zinc-based and copper-based layers. The first two steps of such a process are identical to those of Example 1, but the third layer is plated from a bath containing copper sulphate solution as follows:
Such a bath produces a diffusion-inhibiting layer of copper, copper oxide and arsenic, and, if an outermost layer of zinc nickel alloy is electro-deposited as in Example 1, a peel strength of 18,63 to 20,10 N/cm (4.8 to 5.2 kp/inch) is achieved with no conversion of the zinc in said outermost layer to yellow brass. Further, as is the case in Example 1, the presence of the nickel in the outermost layer prevents any undercutting on etching, even with aggressive etchants such as ferric chloride.
Clearly the third layer could be plated from a solution similar to that above but without copper to give a weak layer of pure arsenic, while the outermost layer, if desired, could be plated from a conventional zinc sulphate bath or any alternative zinc-containing electrolyte to give a layer of zinc.
1. A method of treating copper foil comprising the steps of depositing onto the foil at least one nodular or dendritic layer of metal to improve the bond strength of the foil with an associated base material, encapsulating said layer with one or more layers of metal and applying over the outermost encapsulating layer a further layer containing zinc characterised in that the or each nodular or dendritic layer is of zinc and is deposited directly onto a matt surface of the foil and in that the further layer comprises an alloy of zinc and nickel or of zinc and cobalt.
2. A method according to claim 1 in which the nodular or dendritic layer of zinc is obtained by the use of a relatively dilute solution of sodium zincate as the electrolyte.
3. A method according to claim 1 or claim 2 in which the metal of the encapsulating layer is one or more of the metals copper, arsenic, bismuth, brass, bronze, nickel, cobalt or zinc, or alloys or co-deposits of said metals.
4. A method of treating copper foil as claimed in any one of claims 1 to 3 in which said further layer comprising an alloy of zinc is nodular or dendritic.
5. A method of treating copper foil as claimed in claim 1 or claim 2 which comprises the steps of depositing onto a matt surface of the copper foil a first nodular or dendritic layer of zinc, depositing a protective layer of cyanide copper over said first nodular or dendritic layer, depositing an encapsulating layer of pyrophosphate copper over said protective layer of cyanide copper and depositing a further nodular or dendritic layer of zinc nickel alloy over said encapsulating layer.
6. A method of treating copper foil as claimed in any one of claims 1 to 5 in which the amount of nickel in the zinc nickel alloy of the further layer falls within the range 3 to 15 % by weight.
7. A method of treating copper foil as claimed in any one of claims 1 to 6 which includes the step of depositing a diffusion-inhibiting layer of metal underlying said further layer comprising zinc alloy.
8. A method of treating copper foil as claimed in claim 7 in which the diffusion-inhibiting layer contains arsenic.
9. A method of treating copper foil as claimed in claim 7 in which the diffusion-inhibiting layer comprises an alloy of copper with arsenic.
10. A laminate comprising a dielectric substrate to which is bonded copper foil treated by the method according to any one of the preceding claims.
1. Verfahren zum Behandeln von Kupferfolie, das aufweist die Shritte der Abscheidung wenigstens einer kugeligen oder dentritischen Schicht aus Metall auf der Folie zur Verbesserung der Bindefestigkeit der Folie mit einem mit ihr verbundenen Trägermaterial des Einkapselns dieser Schicht mit einer oder mehreren Schicht(en) aus Metall und des Aufbringens einer weiteren zinkhaltigen Schicht auf die äußerste einkapselnde Schicht, dadurch gekennzeichnet, daß die oder jede kugelige oder dentritische Schicht aus Zink besteht und direkt auf einer matten Oberfläche der Folie abgelagert wird und daß die weitere Schicht eine Legierung von Zink und Nickel oder von Zink und Kobalt enthält.
2. Verfahren nach Anspruch 1, bei dem die kugelige oder dentritische Schicht durch Verwendung einer verhältnismäßig verdünnten Lösung von Natriumzinkat als Elektrolyt erhalten wird.
3. Verfahren nach Anspruch 1 oder 2, bei dem das Metall der einkapselnden Schicht eines oder mehr aus der Gruppe Kupfer, Arsen, Wismut, Messing, Bronze, Nickel, Kobalt oder Zink oder Legierungen oder Mischabscheidungen dieser Metalle ist.
4. Verfahren zum Behandeln von Kupferfolie, wie in einem der Ansprüche 1 bis 3 beansprucht, bei dem die weitere zinkhaltige Schicht kugelig oder dentritisch ist.
5. Verfahren zum Behandeln von Kupferfolie, wie in Anspruch 1 oder Anspruch 2 beansprucht und umfassend die Schritte der Abscheidung einer ersten kugeligen oder dentritischen Schicht aus Zink auf einer matten Oberfläche der Kupferfolie, der Abscheidung einer Schutzschicht aus Kupferzyanid über der ersten kugeligen oder dentritischen Schicht, der Abscheidung einer einkapselnden Schicht aus Kupferpyrophosphat über der Schutzschicht aus kupferzyanid und der Abscheidung einer weiteren kugeligen oder dentritischen Schicht aus Zink-Nickel-Legierung über der einkapselnden Schicht.
6. Verfahren zum Behandeln von Kupferfolie wie in einem der Ansprüche 1 bis 5 beansprucht, bei dem die Menge des Nickels in der Legierung der weiteren Schicht in den Bereich von 3 bis 15 Gewichtsprozent fällt.
7. Verfahren zum behandeln von Kupferfolie, wie in einem der Ansprüche 1 bis 6 beansprucht, das den Schritt der Abscheidung einer diffusionshemmenden Schicht aus Metall, die unter der weiteren zinkhaltigen Schicht liegt, einschließt.
8. Verfahren zum Behandeln von Kupferfolie, wie in Anspruch 7 beansprucht, bei dem die diffusionshemmende Schicht Arsen enthält.
9. Verfahren zum Behandeln von Kupferfolie, wie in Anspruch 7 beansprucht, bei dem die diffusionshemmende Schicht eine Legierung von Kupfer mit Arsen enthält.
10. Laminat, das ein dielektrisches Substrat aufweist, an das eine nach dem Verfahren nach einem der vorhergehenden Ansprüche behandelte Kupferfolie gebunden ist.
1. Procédé de traitement d'une feuille de cuivre, selon lequel on dépose sur la feuille au moins une couche nodulaire ou dendritique de métal pour améliorer la force de la liaison de la feuille avec un matériau de base associé, on encapsule ladite couche par une ou plusieurs couches de métal et on applique sur la couche la plus externe de capsulage une autre couche contenant du zinc, caractérisé on ce que la ou chaque couche nodulaire ou dendritique est du zinc et est déposée directement sur une surface matie de la feuille, et en ce que ladite autre couche comprend un alliage de zinc et de nickel ou de zinc et de cobalt.
2. Procédé selon la revendication 1, dans lequel la couche nodulaire ou dendritique de zinc est obtenue par utilisation d'une solution relativement diluée de zincate de sodium comme électrolyte.
3. Procédé selon l'une des revendications 1 et 2, dans lequel le métal de la couche d'encapsulage est un au moins dans le groupe du cuivre, de l'arsenic, du bismuth, du laiton, du bronze, du nickel, du cobalt ou du zinc, ou des alliages ou co-dépôts desdits métaux.
4. Procédé de traitement d'une feuille de cuivre selon l'une des revendications 1 à 3, selon lequel landite autre couche comprenant un alliage de zinc est nodulaire ou dendritique.
5. Procédé de traitement d'une feuille de cuivre selon l'une des revendications 1 et 2, dans lequel on dépose sur une surface matie de la feuille de cuivre une première couche de zinc nodulaire ou dendritique, on dépose une couche protectrice de cyanure de cuivre sur ladite première couche nodulaire ou dendritique, on dépose une couche de capsulage de pyrophosphate de cuivre sur ladite couche protectrice de cyanure de cuivre, et on dépose une autre couche nodulaire ou dendritique d'un alliage de zinc nickel sur ladite couche de capsulage.
6. Procédé de traitement d'une feuille de cuivre selon l'une des revendications 1 à 5, dans lequel la quantité de nickel dans l'alliage de zinc nickel de ladite autre couche se trouve située dans la gamme de 3 à 15% en poids.
7. Procédé de traitement d'une feuille de cuivre selon l'une des revendications 1 - 6, incluant l'étape du dépôt d'une couche d'inhibition de la diffusion d'un métal en dessous de ladite autre couche contenant un alliage de zinc.
8. Procédé de traitement d'une feuille de cuivre selon la revendication 7, dans lequel la couche d'inhibition de la diffusion contient de l'arsenic.
9. Procédé de traitement d'une feuille de cuivre selon la revendication 7, dans lequel la couche d'inhibition de la diffusion comporte une alliage de cuivre avec de l'arsenic.
10. Stratifé comprenant un substrat diélectrique auquel est liée une feuille de cuivre traitée selon le procédé conforme à l'une quelconque den revendications précédentes.